An efficient and broadly applicable rhodium‐catalyzed direct ortho‐arylation of anilines with aryl iodides relying on readily available aminophosphines as traceless directing groups is reported. Its scope and functional group compatibility were both found to be quite broad as a large variety of both aminophosphines and (hetero)aryl iodides, including complex ones, could be utilized. The ortho‐arylated anilines could be obtained in high average yields, without any competing diarylation and with full regioselectivity, which constitutes a major step forward compared to other processes. The reaction is moreover not limited to aryl iodides, as an aryl bromide and a triflate could be successfully used, and could be extended to diarylation. Mechanistic studies revealed the key and unique role of the aminophosphine, acting not only as a substrate but also as a ligand for the rhodium catalyst.

中文翻译：

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铑催化苯胺的直接邻芳基化

据报道，一种有效且广泛适用的铑催化苯胺与芳基碘化物的直接邻位芳基化反应，依赖于容易获得的氨基膦作为无痕导向基团。其范围和官能团相容性都非常广泛，因为可以使用多种氨基膦和（杂）芳基碘化物，包括络合物。邻芳基化苯胺可以以高平均产率获得，无需任何竞争性二芳基化，并且具有完全的区域选择性，这与其他工艺相比是向前迈出的重要一步。此外，该反应不限于芳基碘化物，因为可以成功地使用芳基溴化物和三氟甲磺酸酯，并且可以扩展到二芳基化。机理研究揭示了氨基膦的关键和独特作用，它不仅充当底物，而且充当铑催化剂的配体。